Role of halogen bonding in clathrate formation of tetra- and hexasalicylides derived from halogenated salicylic acids

Tanaka, Kōichi; Hori, Kyosuke; Tsuyuhara, Shinya; Motoki, Shoichi; Shide, Sayuri; Arakawa, Ryuichi; Caira, Mino R.

doi:10.1016/j.tet.2012.11.057

Cited by 15 publications

(11 citation statements)

References 11 publications

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“…In all cases, the guest solvent was released in a stepwise manner, and endotherm peak temperatures, T p , for highly preferred guest compounds are expectedly higher than those for guest solvents less preferred. Furthermore, it was previously noted that the stability of the host 2 ·2pyridine complex was, in all likelihood, low owing to the nature of the guest accommodation, that is, in open channels . This is confirmed here, where T p values for the release of pyridine are considerably lower than for the other cavity-occupying guest solvents with this host compound.…”

Section: Results and Discussionsupporting

confidence: 85%

“…Furthermore, it was previously noted that the stability of the host 2•2pyridine complex was, in all likelihood, low owing to the nature of the guest accommodation, that is, in open channels. 20 This is confirmed here, where T p values for the release of pyridine are considerably lower than for the other cavity-occupying guest solvents with this host compound.…”

Section: Crystal Growth and Designsupporting

confidence: 77%

“…All the guest compounds in the four complexes of host 2 experience discrete cavity occupation with the exception of pyridine, which is accommodated in multidirectional, infinite, and open channels along the directions [100], [111], and [1̅11]. It has been reported by Tanaka et al that the relative thermal stabilities of the complexes of a particular host compound are dependent on whether the guest molecules are accommodated in channels or discrete cavities, with lower stabilities being associated with the former type. The discrimination displayed by 2 for pyridine may therefore be as a result of the channel occupation experienced by this guest compound.…”

Section: Results and Discussionmentioning

confidence: 99%

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Crystal X-ray Diffraction and Molecular Modeling Considerations Elucidate the Factors Responsible for the Opposing Host Behavior of Two Isostructural Xanthenyl- and Thioxanthenyl-Derived Host Compounds

Barton

McCleland

Caira

et al. 2019

Crystal Growth & Design

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In this work, we compare the host behavior of two structurally related compounds, N,N’-bis(9-phenyl-9-xanthenyl)ethylenediamine and N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine when each one was recrystallized from mixtures of guest solvents pyridine, morpholine, piperidine, and dioxane. (These solvents were clathrated individually in single solvent experiments.) In these conditions, the two hosts displayed distinctly opposing selectivities: when employing an equimolar quaternary guest mixture, the resulting mixed complex of the oxygen host analogue contained a significant amount of dioxane (68%) and only 8% pyridine, while the sulfur host derivative discriminated inordinately against dioxane (12%) in favor of pyridine (57%). These results were more remarkable when considering the crystal packing of the two apohost compounds, which revealed them to be isostructural. The reasons for the opposing host behaviors were explored through detailed crystal X-ray diffraction and computational studies at the molecular mechanics and density functional theory levels. Furthermore, thermal analyses indicated that complexes containing preferred guest solvents possessed increased thermal stabilities. Finally, the two host compounds were allowed to compete by dissolving equimolar mixtures of these in each of the heterocyclic guest solvents, and the results of these experiments were related back to their relative selectivity preferences.

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Section: Results and Discussionsupporting

confidence: 85%

Section: Crystal Growth and Designsupporting

confidence: 77%

Section: Results and Discussionmentioning

confidence: 99%

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Crystal X-ray Diffraction and Molecular Modeling Considerations Elucidate the Factors Responsible for the Opposing Host Behavior of Two Isostructural Xanthenyl- and Thioxanthenyl-Derived Host Compounds

Barton

McCleland

Caira

et al. 2019

Crystal Growth & Design

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“…8 In the latter case, complete disruption of the host framework, necessitating a higher temperature, is required to release the guests, while channel-occupying guests are able to diffuse out at lower temperatures. Our findings from the thermal stability studies showed that the pyridine complex is less stable than the two methylpyridine complexes.…”

Section: Single Crystal X-ray Diffraction Analyses Of the 2$pyridinementioning

confidence: 99%

A computational, X-ray crystallographic and thermal stability analysis of TETROL and its pyridine and methylpyridine inclusion complexes

et al. 2013

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“…Guest enclathration within isolated voids often results in high thermal stability of the crystals of the inclusion compound, but for the present series, the onset temperatures for crystal desolvation determined by thermogravimetry span a relatively low range of ∼50–80 °C, which (except in the case of 1 · 2b ) we attribute to the general lack of cohesion among the enclathrating host molecules.…”

Section: Resultsmentioning

confidence: 59%

Clathrates of TETROL: Further Aspects of the Selective Inclusion of Methylcyclohexanones in Their Energetically Unfavorable Axial Methyl Conformations

Barton¹,

Caira

Hosten³

et al. 2015

J. Org. Chem.

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(+)-(2R,3R)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (TETROL) functions as a highly efficient host for the inclusion of cyclohexanone and 2-, 3-, and 4-methylcyclohexanone, all with 1:1 host/guest ratios. Most extraordinarily, the 3- and 4-methyl isomers are uniquely included in their higher energy axial methyl conformations rather than as their more energetically favorable equatorial analogues. In contrast, 2-methylcyclohexanone is included more conventionally in the equatorial methyl conformation. During recrystallization of TETROL from racemic 2- and 3-methylcyclohexanone, some preference is shown by the host for the (R)-enantiomer. In the latter case, this is attributed to a much stronger H-bond between a hydroxyl group of TETROL and the carbonyl group of the (R)-enantiomer (O···O 2.621(2) Å) compared with a significantly weaker H-bond to the (S)-enantiomer (3.125(8) Å). In the former instance, hydrogen-bond strengths to both enantiomers are similar, but the (R)-enantiomer engages in three (guest)CH···π(host) and three (guest)H···Car(host) contacts, whereas fewer interactions of these types are observed for the (S)-enantiomer. Calculations of geometries of the guest cyclohexanones were determined at the MP2/6-311++G(2df,2p) level and compared with those obtained at the G3(MP2) level. Finally, an interesting correlation between crystal packing indices for the three methylcyclohexanone clathrates and their respective desolvation onset temperatures was identified.

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Role of halogen bonding in clathrate formation of tetra- and hexasalicylides derived from halogenated salicylic acids

Cited by 15 publications

References 11 publications

Crystal X-ray Diffraction and Molecular Modeling Considerations Elucidate the Factors Responsible for the Opposing Host Behavior of Two Isostructural Xanthenyl- and Thioxanthenyl-Derived Host Compounds

Crystal X-ray Diffraction and Molecular Modeling Considerations Elucidate the Factors Responsible for the Opposing Host Behavior of Two Isostructural Xanthenyl- and Thioxanthenyl-Derived Host Compounds

A computational, X-ray crystallographic and thermal stability analysis of TETROL and its pyridine and methylpyridine inclusion complexes

Clathrates of TETROL: Further Aspects of the Selective Inclusion of Methylcyclohexanones in Their Energetically Unfavorable Axial Methyl Conformations

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